Azo-dyestuffs



Patented Feb. 27, 1934 AZO-DYESTUFFS Gerald Bonhote and Carl Apotheker, Basel, Switzerland, assignors to Society of Chemical Industry in Basle, Basel, Switzerland No Drawing.

Application July 8, 1933, Serial No.

679,578. In Switzerland July 13, 1932 4 Claims.

According to this invention new dyestufis are made by coupling an arylide of 2:3-hydroxynaphthoic acid with a diazoor poly-azo-compound derived from a base of the general formula Rx-III-Ri Ra in which R1, R2 and R3 may be any aryl residues, at least one of which contains a diazotizable amino-group, and which may contain various substituents.

The dyestufis thus obtained which correspond with the general formula wherein R1, R2, R3 and R4 stand for aromatic nuclei of the benzene or naphthalene series, are dark powders applicable for coloring varnishes, lacquers or for use as pigments. They dissolve in organic solvents, for example pyridine or glacial acetic acid, to red to Bordeaux, violet, blue, green and black solutions. Particularly valuable dyeings are obtained when the new dyestuffs are produced on the fiber in known manner. The Bordeaux to violet, blue, green and black dyeings thus produced are characterized by their fullness and their properties of fastness.

The following examples illustrate the invention:

Example 1 26 parts by weight of para-aminotriphenylamine are diazotized in the usual manner. The solution thus obtained is introduced, if necessary after filtration, into one of 26.3 parts oi 2:3-hy- ,droxynaphthoic acid-anilide, parts of caustic soda solution of 30 per cent. strength, 50 parts of calcined sodium carbonate and 2000 parts of water. The dyestuff thus formed of the formula is a blue precipitate which is filtered, washed and dried.

Example 2 Cotton yarn is impregnated with a grounding made by dissolving 5.5 grams of 2.3-hydroxynaphthoic acid-para-chloranilide in 300 cc. of hot water with addition of 11 cc. of caustic soda solution of 30 per cent, strength and 8 cc. or Turkey red oil, the whole being then diluted to 1 liter. The goods are then wrung out and developed in a neutralized solution containing 2.5 grams per liter of diazotized para-aminotriphenylamine. In this manner there is obtained a pure greenish-blue dyeing of very good properties of fastness.

Similar results are obtained in the dyeing or printing of piece-goods.

If it is desired to produce the dyestuffs of this invention on wool, it is advantageous to use such baths which contain at least 1 gram of sodium hydroxide in the liter and containing 1.5 to 3 per cent. of the arylide calculated on the weight of the wool.

Example 3 10 grams of cotton yarn are impregnated in 250 cc. of a bath containing 7 grams of 2:3-

hydroxynaphthoic acid-2-methylanilide, 14 cc.

Example 4 of caustic soda solution of 30 per cent. strength,

(which of 2 3-hydroxy-naphthoic amine.

quickly and is very fast. sponds very probably with the formula ylic acid) with para-nitrochlorobenzene with simultaneous elimination of the carboxyl group and reduction of the nitro-compound. The goods are then rinsed and soaped; the dyeing obtained is a very pure blue of very good properties of fast ness. The new dyestuiT corresponds very probably with the formula (RCH:

The material to be printed is foularded with an alkaline solution containing per liter 12 grams acid-3-nitram'lide. After drying, the material is treated with a printing color containing per kilo 8 grams of diazotized 4 amino 2 :5 :4"- trimethoxytriphenyl- The deep, pure blue dyeing develops very The new dyestufl corre- The following table sets forth a number of dyestuffs which may be made in accordance with this invention Diazo component es r. 4-chloro-4-aminotrlplienylarnine-2-carboxyllc acid-ethyl- 4-metl1oxy4-aminotriplienylumine-Q-carboxylic 4-ethoxy-4-an1inotriphenylamine-Z-carboxylic acid-ethyll 2:4 rnethyl-4-aminotrip11enylamihe-Z-carboxylic acid 2:5-dichloro-4-aminotriphenylarnineqerboxylic 2"-xnetlioxy 4- chloro -4- aminotriphenylalnine -2 carbox- N(l-naphtliyl)-4"-on1inorliphenylamine-2-carboxylic l amino triphenylmnine-Z-carboxylic acid-anilide 4'chlor0-4-aminotriphenylamine-2-carboxylio acld-anilide. 4"-1netl1yl-nminotripl:enylamine- 2"-1nethyll-arninoiriphenvlamine- Z-aminotriphenylamine. Q-methoxy 2 aminotriphe 4-an1inotriphenylamine 4-methyl-4-aminotriphenylom 2-methyl-4-aminotriphenylamine 4-chloro-4-aminotriphenylamine.. 2-chloro4-aminotriphenylamine 4-rnetho '-4-aminotriphenylemine 2-meth -4-arnino triphenylarnine ester. 2-chloro-4-cminotriphenylamine-Z-carboxylic acid-ethylester.

2"-methoxy-4 aminotriphenylaminc-2-ca1-boxylic acidethylester.

acidethylester.

ethylester acidethylester.

ylic acid-ethylester.

acidethylester. 2"-methyl-4-cliloro'4-aminotriphenylamine-l-cnrboxylic ocid-ethylester elbylester.

Q-carboxylic acid-aniline. rboxvhcacrdnmhde.

Coupling component Color tint 2:3-hydroxynaphthoic acid-sulfide Red blue 2:3-hydroxynaphth0ic acid-W-chloranrhde Blue. 2:3-hydroxynapl1thoie acid-3-nitran1l1de 31 2:3-hydroxynaphthoic acid-2:4-dirnethylanilid Vi l t, 2:3-hydroxynaphthoic acid-W-ethoxyanilidc Violet. 2:3-hydroxynnphthoic aold-3-niran1llde Green blue. 2 t ll ill? t' tt l" lll ti 2.3- y 1' 1121') 010 201 -me y am 1 e... ue, 2:3-hydr naphthoic aeid-3:4-dicbloranilide 2:3-hydroxynaphthoic acidT-rnethoxyamhda. 2:3-hydr0xynaphth0ic ncid-3nitmnilide... Red blue 2:3-hydroxynaphth0ic acid-4-chloro-2-t0luldlde Bl 2:3-hydroxynophthoic acid-2 :5 -dimeth0xyani li( le Vi l t, ZZZ-EYgIOXYDEWIQltZEOlO acig-gi-ngfithoxy q-toluidule gled blue 23- y roxynap me 2101 -c oronl e 2:3-hydroxynaphthoic acid-3-nitranilide.. Green bl 2:3-hydr0xynaphthoic acid-5-chloro-2-t0lu1d1dc Blue, 2:3-hydroxynaphthoic acid-3-chloranilide R d bl 2:3'hydroxynaphthoic acid-3-methylanilide or Red blue. 2z3-gyalroxynaplhtgoic acig-gzz-lirnlethylginrhde geg glue. 2:3- y roxynap 01c ocl .i 10 0mm 1( e 9 1m 2:3-hydroxynaphthoic acid-3-4-dichloranilide R d Bl 2:3-hydroxynaphthoic acid-3nitranilide Blue.

2:3-hydroxynaphthoic acid-4-methoxyanilide Violet.

2:3 hydroxynaphthoic acid-4-chloranilide Violet.

2:3-hydroxynaphth0ic acid-Y-naphthylamide Red Blue 2:3-hydroxynaphthoic acid-3-nitranilide Bl 2:3-l1ydroxynaphthoic acid4-cl1loro-2"t01uididc Red Blue.

2:3 hydroxynsphthoic acid3-nitranilide Blue.

2:3-hydroxynaphthoic aciG-T-naphthylannide Violet.

2:3-hydroxynaphtl1oic acid-3:4-dichloranilide Red Blue.

2:3-hydroxynaphthoic acid-4-metl1oxyanilide Red Blue.

2:3-hydroxynaphthoic acid-2 :5-dimetl1ylani1ide Red blue.

2:3-hydroxynaphtl1oic acid-3chl0ranilide Red blue.

2:3-hydroxynaphtlioic acidV-naphthylamide Red blue. 2:3-hydroxynaphtboic eold-2-ethoxy-5-tolui(l1de. Violet.

.i-l ilygroxynapgtgoic acifll-gr-chloro-i5gt0lu1d1de gag glue. y roxynap t oic oci -nitrani i e e ue. Z-hydroxynaphthoic acid-anilide Bordeamz. 3-hydroxynaphthoic acid-4-ch1oranilide Bordeaux.

The formula of dyestuff 19 is very probably:

HI IQ.

(IJH s The formula of dyestufi 40 is very probably:-

OOHs

i HNOC1.

What we claim is:

1. The azo-dyestuffs of the general formula wherein R1, R2, R3 and R4 stand for aromatic nuclei of the benzene or naphthalene series, which dyestufis form dark powders dissolving in organic solvents to blue-red to violet, blue and black solutions, and, when produced on the fiber, especially cotton fiber, dye the same fast red to Bordeaux, violet, blue, green and black tints.

2. The azo-dyestufis of the general formula wherein R1 and R2 stand for benzene nuclei containing alkoxy groups, R3 stands for an aromatic nucleus of the benzene series, and R4 for an aromatic nucleus of the benzene or naphthalene series, which dyestuffs form dark powders dissolving in organic solvents to violet to blue and green-blue solutions, and, when produced on the fiber, especially cotton fiber, dye the same' fast violet to blue and green-blue tints.

4. The azo-dyestufis of the general formula OGHs wherein R stands for an aromatic nucleus of the benzene or naphthalene series, which dyestuffs form dark powders dissolving in organic solvents to violet to blue solutions, and, when produced on textiles, especially cotton, dye the same fast blue to green-blue tints.

GERALD BONl-IOTE.

CARL APOTHEKER. 

